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| United States Patent |
6,190,677
|
|
Remy
|
February 20, 2001
|
Process for preparing a photochromic compound and a cosmetic composition
thereof
Abstract
A process for preparing a photochromic compound and/or improving the
photochromic properties of a photochromic compound selected from metal
oxides, hydrated metal oxides and metal oxide/hydrate complexes by
heat-treating the photochromic compound in the presence of at least one
metallic component such as an oxide or hydroxide of lithium, sodium and/or
potassium, the photochromic compound obtained using this process, and the
cosmetic composition comprising it.
| Inventors:
|
Remy; Christophe (Paris, FR)
|
| Assignee:
|
L'Oreal ()
|
| Appl. No.:
|
007751 |
| Filed:
|
January 15, 1998 |
Foreign Application Priority Data
| Current U.S. Class: |
424/401; 424/61; 424/64; 424/70.7 |
| Intern'l Class: |
A61K 006/00; A61K 007/00; A61K 007/04; A61K 007/025 |
| Field of Search: |
424/61,401,450,64,70.7,70.1,59
514/937,938,944,844,845
|
References Cited
U.S. Patent Documents
| 4572618 | Feb., 1986 | Abraham et al. | 350/354.
|
| 5762915 | Jun., 1998 | Saito et al. | 424/59.
|
| 5858338 | Jan., 1999 | Piot et al. | 424/70.
|
| 5989573 | Jun., 1998 | Remy | 424/401.
|
| Foreign Patent Documents |
| 0 624 553 | Nov., 1994 | EP.
| |
Other References
Derwent Abstract No. 93-070851 of JP 05-017152.
|
Primary Examiner: Page; Thurman K.
Assistant Examiner: Howard; S.
Attorney, Agent or Firm: Finnegan, Henderson, Farabow, Garrett & Dunner, L.L.P.
Claims
I claim:
1. A process for preparing a photochromic compound having a parameter
.DELTA.(.DELTA.E) of at least 7, comprising
heat-treating at least one photochromic compound selected from metal
oxides, hydrated metal oxides and metal oxide/hydrate complexes at a
temperature ranging from 400 to 1000.degree. C. in the presence of at
least one metallic component selected from oxides and hydroxides of
lithium, sodium and potassium.
2. A process according to claim 1, wherein said at least one photochromic
compound is selected from oxides and hydrated oxides of titanium, niobium,
silicon, aluminium, zinc, hafnium, thorium, tin, thallium, zirconium,
beryllium, cobalt, calcium and magnesium.
3. A process according to claim 1, wherein said at least one photochromic
compound is titanium dioxide rendered photochromic by a metal selected
from iron, chromium, copper, nickel, manganese, cobalt, molybdenum, and
salts thereof.
4. A process according to claim 3, wherein said salts are selected from
sulphates, chlorates, nitrates and acetates.
5. A process according to claim 1, wherein said at least one metallic
component is selected from oxides and hydroxides of lithium.
6. A process according to claim 1, wherein said at least one metallic
component is present in a concentration ranging from 0.01 to 30% by weight
of metal ions with respect to the total weight of said photochromic
compound.
7. A process according to claim 6, wherein said at least one metallic
component is present in a concentration ranging from 0.02 to 20% by weight
of metal ions with respect to the total weight of said photochromic
compound.
8. A process according to claim 1, wherein said heat treating is carried
out at a temperature ranging from 600 to 900.degree. C.
9. A process according to claim 1, wherein said heat treating is carried
out for a time ranging from 10 minutes to 6 hours.
10. A process according to claim 9, wherein said heat treating is carried
out for a time ranging from 2 to 5 hours.
11. A photochromic compound obtained according to claim 1.
12. A photochromic compound according to claim 11, wherein said parameter
.DELTA.(.DELTA.E) is at least 10.
13. A photochromic compound according to claim 12, wherein said parameter
.DELTA.(.DELTA.E) is at least 12.
14. A cosmetic composition comprising at least one compound according to
claim 11.
15. A cosmetic composition according to claim 14, wherein said at least one
compound is present in a concentration ranging from 0.01 to 30% by weight,
relative to the total weight of said cosmetic composition.
16. A cosmetic composition according to claim 15, wherein said at least one
compound is present in a concentration ranging from 1 to 15% by weight,
relative to the total weight of said cosmetic composition.
17. A cosmetic composition according to claim 14, wherein said cosmetic
composition is in the form of an optionally thickened or gelled
suspension, dispersion or solution in solvent or aqueous-alcoholic medium;
an oil-in-water, water-in-oil or multiple emulsion; a gel or a foam; an
emulsified gel; a dispersion of vesicles; a two-phase or multi-phase
lotion; a spray; a free, compact or loose powder; or an anhydrous paste.
18. A cosmetic composition according to claim 17, wherein said vesicles are
lipid vesicles.
19. A cosmetic composition according to claim 14, wherein said cosmetic
composition is in the form of a care and/or make-up product for the skin;
a suncare or self-tanning product; or a haircare product.
20. A cosmetic composition according to claim 19, wherein said make-up
product is in the form of a lip composition, a foundation, a blusher or
eye-shadow, a free or compact powder, a tinted cream, an eye-liner, a
mascara, or a nail varnish.
21. A process for improving the parameter .DELTA.(.DELTA.E) of at least one
photochromic compound selected from metal oxides, hydrated metal oxides
and metal oxide/hydrate complexes, said process comprising
heat-treating, for the purpose of improving said parameter
.DELTA.(.DELTA.E), said at least one photochromic compound at a
temperature ranging from 400 to 1000.degree. C. in the presence of at
least one metallic component selected from oxides and hydroxides of
lithium, sodium and potassium.
22. A process according to claim 21, wherein said at least one photochromic
compound is selected from oxides and hydrated oxides of titanium, niobium,
silicon, aluminium, zinc, hafnium, thorium, tin, thallium, zirconium,
beryllium, cobalt, calcium and magnesium.
23. A process according to claim 22, wherein said at least one photochromic
compound is titanium dioxide rendered photochromic by a metal selected
from iron, chromium, copper, nickel, manganese, cobalt, molybdenum, and
salts thereof.
24. A process according to claim 23, wherein said salts are selected from
sulphates, chlorates, nitrates and acetates.
25. A process according to claim 21, wherein said at least one metallic
component is selected from oxides and hydroxides of lithium.
26. A process according to claim 21, wherein said at least one metallic
component is present in a concentration ranging from 0.01 to 30% by weight
of metal ions with respect to the total weight of said photochromic
compound.
27. A process according to claim 26, wherein said at least one metallic
component is present in a concentration ranging from 0.02 to 20% by weight
of metal ions with respect to the total weight of said photochromic
compound.
28. A process according to claim 21, wherein said heat treating is carried
out at a temperature ranging from 600 to 900.degree. C.
29. A process according to claim 21, wherein said heat treating is carried
out for a time ranging from 10 minutes to 6 hours.
30. A process according to claim 29, wherein said heat treating is carried
out for a time ranging from 2 to 5 hours.
31. A photochromic compound obtained according to claim 21.
32. A photochromic compound according to claim 31, wherein said parameter
.DELTA.(.DELTA.E) is at least 10.
33. A photochromic compound according to claim 32, wherein said parameter
.DELTA.(.DELTA.E) is at least 12.
34. A cosmetic composition comprising at least one compound according to
claim 31.
35. A cosmetic composition according to claim 34, wherein said at least one
compound is present in a concentration ranging from 0.01 to 30% by weight,
relative to the total weight of said cosmetic composition.
36. A cosmetic composition according to claim 35, wherein said at least one
compound is present in a concentration ranging from 1 to 15% by weight,
relative to the total weight of said cosmetic composition.
37. A cosmetic composition according to claim 34, wherein said cosmetic
composition is in the form of an optionally thickened or gelled
suspension, dispersion or solution in solvent or aqueous-alcoholic medium;
an oil-in-water, water-in-oil or multiple emulsion; a gel or a foam; an
emulsified gel; a dispersion of vesicles; a two-phase or multi-phase
lotion; a spray; a free, compact or loose powder; or an anhydrous paste.
38. A cosmetic composition according to claim 37, wherein said vesicles are
lipid vesicles.
39. A cosmetic composition according to claim 34, wherein said cosmetic
composition is in the form of a care and/or make-up product for the skin;
a suncare or self-tanning product; or a haircare product.
40. A cosmetic composition according to claim 39, wherein said make-up
product is in the form of a lip composition, a foundation, a blusher or
eye-shadow, a free or compact powder, a tinted cream, an eye-liner, a
mascara, or a nail varnish.
Description
The present invention relates to the improvement of the photochromic
properties of an initially photochromic compound, and to its application
in the field of cosmetic compositions, in particular.
Cosmetic compositions, in particular make-up compositions such as free or
compact powders, foundations, blushers or eye-shadows, lip compositions or
nail varnishes, comprise a suitable vehicle and various colorants intended
to impart some degree of color to the compositions before and/or after
they are applied to the skin, the mucous membranes, the mucocutaneous
tissues and/or parts of the exoskeleton, for example the nails or the
hair.
A fairly limited range of colorants is presently used to create colors, in
particular lakes, inorganic pigments or pearlescent pigments. Lakes allow
vivid colors to be obtained, but are for the most part unstable with
respect to light, temperature or pH. Some of them also have the drawback
of staining the skin unattractively after they have been applied, as a
result of the colorant being leached. Conversely, inorganic pigments, in
particular inorganic oxides, are highly stable but give somewhat dull and
pale colors. In order to obtain colored effects, use may also be made of
pearlescent pigments whose colors are varied, albeit never intense, which
make it possible to obtain iridescent but most often fairly weak effects.
It has therefore been proposed to use photochromic compounds in make-up or
haircare compositions, so as to obtain attractive and varied changes in
the color effect of make-up for the skin and/or the hair.
Photochromic compounds are compounds which have the property of changing
color when they are exposed to a light source, then of returning to their
initial color, or a similar color, when they are no longer being exposed.
In particular, compounds of this type have a particularly advantageous
application in cosmetic compositions, in particular in make-up
compositions such as foundations and blushers or eye-shadows. Indeed, it
has been found that the make-up effect of skin which has been made up
differs depending on whether the illumination is natural or artificial.
Thus, make-up applied under artificial illumination will appear lighter
under natural light. Conversely, make-up applied out of doors will appear
darker in a place where the illumination is artificial.
The photochromic properties of a compound can be characterized using two
parameters, calculated on the basis of measuring the trichromatic
coordinates (L, a and b), in the following way.
A compound which initially has the coordinates (L0, a0, b0) will be
considered.
The compound is firstly exposed to a light source for 30 minutes under
standard conditions, then the new coordinates (L30, a30 and b30) are
measured, these coordinates reflecting the color change due to the
exposure. A first parameter .DELTA.E30 can be calculated which reflects
the ability of a compound to take on a color different from the original
one:
.DELTA.E30=[(L30-L0).sup.2 +(a30-a0).sup.2 +(b30-b0).sup.2 ].sup.1/2
The compound which has been exposed for 30 minutes is secondly placed in
complete darkness for 30 minutes, then the new coordinates (L60, a60 and
b60) are measured.
A second parameter .DELTA.E60 can be calculated which reflects the color
change with respect to the situation before exposure:
.DELTA.E60=[(L60-L0).sup.2 +(a60-a0).sup.2 +(b60-b0).sup.2 ].sup.1/2
The value .DELTA.(.DELTA.E), equal to the absolute value of the difference
between .DELTA.E60 and .DELTA.E30, reflects the capacity of a compound to
return, after exposure and darkness, to a color similar to that of the
initial state, that is to say before exposure.
The prior art has, in particular, proposed the use in cosmetics of organic
photochromic compounds, for example compounds of the spiropyran or
naphthoxazine families.
These photochromic compounds are particularly advantageous since they
enable the support to which they are applied to change color rapidly when
the support is exposed to UV, for example, with rapid return to the
initial color when it is no longer being exposed to UV.
Mention may thus be made of French Patent Application FR 1 604 929, which
describes cosmetic compositions, in particular for the hair, in aerosol
form which contain phototropic compounds such as nitrobenzylpyradines,
thiosemi-carbazones or spiropyran derivatives. After these compositions
have been sprayed onto the hair and exposed to sunlight, a blue-violet
coloration is obtained which returns to pale yellow in darkness.
Cosmetic compositions comprising particular inorganic photochromic
compounds, selected from metal oxides, their hydrated forms and their
complexes, have also been proposed, for example by European Patent
Application EP 359 909. In particular, this document mentions the use of
titanium oxide, treated so as to make it photochromic, in make-up
compositions such as powders and foundations.
Further, U.S. Pat. No. 5,176,905 discloses a process for obtaining a
photochromic titanium oxide by mixing iron hydroxide (FeOOH) and titanium
dioxide, and calcining at 750-850.degree. C.
In addition, European Patent Application EP 624 553 discloses a process for
preparing titanium oxide having improved photochromism, this process
involving dissolving an organotitanium compound and an organic compound
comprising at least one metal, in an organic solvent, then in hydrolysing
the mixture, recovering the hydrolysate and in calcining it at a
temperature of 550-700.degree. C. This produces a photochromic titanium
oxide having a color difference which can be quantified using the
parameter .DELTA.E, the value of which is at least 10. The value .DELTA.E
is the measured difference between the chromaticity before exposure and
the chromaticity after exposure for 1 hour, under UV at 2 mW/cm.sup.2.
Furthermore, Japanese Patent Application JP 05/017152 discloses a process
for preparing a photochromic titanium oxide, involving mixing
organotitanium compounds with at least one metal selected from iron,
chromium, copper, nickel, vanadium or manganese, then in sintering the
mixture in the presence of sodium compounds. It is thus possible to obtain
a parameter .DELTA.E which is improved in comparison with the prior art,
and is in particular greater than 10. The parameter .DELTA.E is calculated
in the same way as in EP 624 553.
In the latter two documents, the improved parameter .DELTA.E reflects the
ability of a compound to change color when exposed to light. This document
makes absolutely no mention of any improvement of the parameter
.DELTA.(.DELTA.E), which reflects the ability of the compound to return to
a state similar to the initial state.
However, it has been observed that, even though they make it possible to
obtain an appreciable change in the color of the make-up, that is to say a
relatively large .DELTA.E, the prior art photochromic compounds, in
particular the inorganic compounds, nevertheless have the following
drawback: when it is no longer being exposed to light, the color of the
make-up does not always return acceptably to its initial color, and in
particular does not return completely to a color identical to the initial
color. After a cycle of exposure and darkness, the photochromic compound
has a color substantially different from its initial color before
exposure. The "relaxation of the photochromic compound in the dark" can
thus be considered as weak or low. For these compounds, this is
characterized by a small value of .DELTA.(.DELTA.E), of the order of 3-4.
The object of the present invention is to provide a particular process for
improving photochromism, in particular improving the value
.DELTA.(.DELTA.E) of an initially photochromic compound, while maintaining
a satisfactory value .DELTA.E30, that is to say one which is at least of
equal value, and often improved, that is to say as high as possible.
The present invention therefore relates to a process for preparing a
photochromic compound having a parameter .DELTA.(.DELTA.E) greater than or
equal to 7, in which a photochromic compound of the metal oxide, hydrated
metal oxide or metal oxide and/or hydrate complex type is heat-treated at
a temperature ranging from 400 to 1000.degree. C. in the presence of a
metallic component selected from the oxides and/or hydroxides of lithium,
sodium and/or potassium.
The invention also relates to a process for improving the parameter
.DELTA.(.DELTA.E) of a photochromic compound of the metal oxide, hydrated
metal oxide or metal oxide and/or hydrate complex type, involving
heat-treating the compound at a temperature ranging from 400 to
1000.degree. C. in the presence of a metallic component selected from the
oxides and/or hydroxides of lithium, sodium and/or potassium.
The invention further relates to the photochromic compound of the metal
oxide, hydrated metal oxide or metal oxide and/or hydrate complex type,
which can be obtained using one of these processes.
The invention further relates to cosmetic compositions comprising the
compound.
Without being limited by the present explanation, the photochromism of a
doped titanium oxide may be illustrated as follows. A photochromic
titanium oxide of the anatase form will be considered, which is doped with
iron atoms of valency 3+ and 4+ substituting for titanium atoms.
When exposed to UV, it can be considered that, by being converted into
Fe.sup.4+, an Fe.sup.3+ cation will give up an electron to an entity X
which will be converted into an entity X.sup.-, responsible for the color
change of the photochromic compound. X may be considered as an oxygen
vacancy in the anatase lattice. It may be assumed that, during a second
phase, electrons in the valence band of the titanium oxide will then be
moved to the conduction band, consequently generating both free electrons
and electron vacancies in the valence band, which are also referred to as
positive "holes", i.e., a vacant state in an energy band, corresponding to
a region with a negative charge in deficit. It is moreover known that the
electrons and the vacancies for the most part tend to recombine. The final
phase, the phase of "relaxation in the dark", corresponding to the return
to the initial color, takes place through the conversion of X.sup.- to X,
with an electron being released for the lattice, for example in a defect
of the anionic type associated with an oxygen vacancy, or to an Fe.sup.4+
formed during the exposure.
The following explanation may be proposed in order to illustrate the
mechanism allowing the photochromic properties of a given compound to be
improved. A photochromic titanium oxide of the anatase form will be
considered, which is doped with iron atoms of valency 3+ and 4+, these
being substituted for the titanium of valency 4+ in the anatase crystal
lattice. In order to keep the compound electrically neutral, charge
compensation must take place, most likely by the creation of oxygen
vacancies.
When the process according to the invention is applied, that is to say when
the doped titanium oxide is heat-treated in the presence of small ions
with weak positive charge, it may be assumed that:
in order to compensate for the addition of positive charge, some of the
iron atoms of valency 4+ are converted into iron of valency 3+, releasing
an electron for X which is converted into X.sup.-. This provides an
increase in .DELTA.E30.
in order to compensate for the addition of positive charge, the number of
oxygen vacancies and associated anionic defects increases; however, the
relaxation in the dark takes place through the release of an electron from
X.sup.- to a defect of this type; since the number of these defects is
increased by virtue of the process of the invention, the return to the
initial color is improved, whence an improved parameter .DELTA.(.DELTA.E).
by virtue of the process according to the invention, the iron 3+ in the
anatase tends to be preferentially close to an oxygen vacancy; the
exchanges of electrons between the iron and the vacancy will therefore be
facilitated, whence an increase in the photochromism (.DELTA.E30 and
.DELTA.(.DELTA.E)).
The process according to the invention therefore involves heat-treating a
photochromic compound of the metal oxide, hydrated metal oxide or metal
oxide and/or hydrate complex type in the presence of a metallic component
selected from oxides and/or hydroxides of lithium, sodium and/or
potassium.
Among the metal oxides, mention may, in particular, be made of oxides of
titanium, niobium, silicon, aluminium, zinc, hafnium, thorium, tin,
thallium, zirconium, beryllium, cobalt, calcium and magnesium. The oxides
and hydrated oxides of titanium, aluminium, zinc, zirconium, calcium and
magnesium are preferred.
More preferably, use will be made of titanium dioxide which can be rendered
photochromic using a metal selected from iron, chromium, copper, nickel,
manganese, cobalt, molybdenum, as such or in the form of a salt such as a
sulphate, a chlorate, a nitrate or an acetate.
The metallic component is preferably selected from the oxides or hydroxides
of lithium. Mention may, in particular, be made of lithium hydroxide LiOH,
and sodium peroxide Na.sub.2 O.sub.2.
The metallic component may be present in a concentration preferably ranging
from 0.01 to 30% by weight of metal ions, more preferably from 0.02 to 20%
by weight, with respect to the weight of photochromic compound to be
treated.
The heat-treatment may be carried out at a temperature preferably ranging
from 400 to 1000.degree. C., more preferably 600-900.degree. C., for
example for a time preferably ranging from 10 minutes to 6 hours, more
preferably from 2 to 5 hours.
This produces a heat-treated photochromic compound whose parameter
.DELTA.(.DELTA.E) is preferably at least equal to 7, more preferably
greater than or equal to 10, even more preferably greater than or equal to
12.
The photochromic compound treated according to the process of the invention
may be incorporated in a cosmetic composition in a quantity which can be
determined easily by the person skilled in the art, on the basis of his
general knowledge, and which may, in particular, range from 0.01 to 30% by
weight with respect to the total weight of the composition, more
preferably 1 to 15% by weight.
The photochromic composition may be in the form of a product to be applied
to the mucous membranes, the mucocutaneous tissues and/or the keratinous
tissues, such as the skin and parts of the exoskeleton (nails, eyelashes,
eyebrows, body hair and head hair). It therefore contains a cosmetically
acceptable medium, that is to say a medium which is compatible with all
the keratinous materials such as the skin, the nails, the hair, the
eyelashes, the eyebrows, the mucous membranes and the mucocutaneous
tissues, and any other cutaneous region of the body and the face. The
medium may comprise or be in the form of, in particular, a suspension, a
dispersion or a solution in solvent or aqueous-alcoholic medium,
optionally thickened or gelled; an oil-in-water, water-in-oil or multiple
emulsion; a gel or a foam; an emulsified gel; a dispersion of vesicles, in
particular lipid vesicles; a two-phase or multi-phase lotion; a spray; a
free, compact or loose powder; an anhydrous paste. The person skilled in
the art will be able to choose the suitable pharmaceutical form, as well
as the method of preparing it, on the basis of general knowledge, while
taking into account both the nature of the constituents which are used, in
particular their solubility in the support, and the application envisaged
for the composition.
When the composition is present in aqueous form, in particular in the form
of a dispersion, an emulsion or an aqueous solution, it may comprise an
aqueous phase which may comprise water, a floral water such as cornflower
water, and/or a mineral water such as water from sources such as Vittel,
Vichy, Uriage, Roche Posay, Bourboule, Enghien-les-Bains, Saint
Gervais-les-Bains, Neris-les-Bains, Allevar-les-Bains, Digne, Lucas,
Maizieres, Neyrac-les-Bains, Lons-le-Saunier, Eaux Bones, Rochefort, Saint
Christau, Fumades and Tercis-les-bains.
The aqueous phase may comprise from 0% to 14% by weight, relative to the
total weight of the aqueous phase, of a C.sub.2 -C.sub.6 lower monoalcohol
and/or of a polyol such as glycerol, butylene glycol, isoprene glycol,
propylene glycol or polyethylene glycol.
When the composition according to the invention is in the form of an
emulsion, it may optionally furthermore comprise a surfactant, preferably
in an amount of from 0.01 to 30% by weight relative to the total weight of
the composition.
Among the anionic surfactants which may be used, alone or as a mixture,
mention may in particular be made of alkali metal salts, ammonium salts,
amine salts or amino alcohol salts of the following compounds: alkyl
sulphates, alkyl ether sulphates, alkylamide sulphates and ether
sulphates, alkylarylpolyether sulphates, monoglyceride sulphates,
alkylsulphonates, alkylamide sulphonates, alkylaryl sulphonates,
.alpha.-olefin sulphonates, paraffin sulphonates, alkyl sulphosuccinates,
alkyl ether sulphosuccinates, alkylamide sulphosuccinates,
alkylsulphosuccinamates, alkyl sulphoacetates, alkyl polyglycerol
carboxylates, alkyl phosphates/alkyl ether phosphates, acyl sarcosinates,
alkylpolypeptidates, alkylamidopolypeptidates, acyl isenthionates, alkyl
laurates. The alkyl or acyl radical in all of these compounds generally
denotes a chain of 12 to 18 carbon atoms. Mention may also be made of
soaps and fatty acid salts such as oleic acid, ricinoleic acid, palmitic
acid, stearic acid, coconut oil acid or hydrogenated coconut oil acid and,
in particular, amine salts such as amine stearates; acyl lactylates in
which the acyl radical comprises 8-20 carbon atoms; carboxylic acids of
polyglycol ethers corresponding to the formula:
Alk--(OCH.sub.2 --CH.sub.2).sub.n --OCH.sub.2 --COOH
in acid or salified form, in which the substituent Alk corresponds to a
straight chain having from 12 to 18 carbon atoms, and in which n is an
integer ranging from 5 to 15.
Among the non-ionic surfactants which may be used, alone or as a mixture,
mention may in particular be made of: polyethoxylated, polypropoxylated or
polyglycerolated fatty acids, alkylphenols and alcohols which have a fatty
chain containing from 8 to 18 carbon atoms; copolymers of ethylene oxide
and of propylene oxide, condensates of ethylene oxide and of propylene
oxide with fatty alcohols, polyethoxylated fatty amides, polyethoxylated
fatty amines, ethanolamides, fatty acid esters of glycol, fatty acid
esters of oxyethylenated or non-oxyethylenated sorbitan, fatty acid esters
of saccharose, fatty acid esters of polyethylene glycol, phosphoric
triesters, fatty acid esters of glucose derivatives; alkyl polyglycosides
and alkylamides of amino sugars; condensation products of an .alpha.-diol,
of a monoalcohol, of an alkylphenol, of an amide or of a diglycolamide
with glycidol or a glycidol precursor.
The composition according to the invention may also comprise preferably
from 0 to 5% by weight, relative to the total weight of the emulsion, of
at least one co-emulsifier which may be selected from oxyethylenated
sorbitan monostearate, fatty alcohols such as stearyl alcohol or cetyl
alcohol, or fatty acid esters of polyols such as glyceryl stearate.
The composition according to the invention may furthermore comprise one or
more thickeners in preferred concentrations ranging from 0 to 6% by
weight, relative to the total weight of the composition, which are
selected from:
polysaccharide biopolymers such as xanthan gum, carob gum, guar gum,
alginates, modified celluloses such as hydroxyethylcellulose,
methylcellulose, hydroxypropylcellulose and carboxymethylcellulose, starch
derivatives, cellulose ether derivatives containing quaternary ammonium
groups, cationic polysaccharides;
synthetic polymers, for instance polyacrylic acids such as polyglyceryl
(meth)acrylate polymers such as HISPAGEL or LUBRAGEL from the companies
Hispano Quimica or Gardian, polyvinylpyrrolidone, polyvinyl alcohol,
crosslinked polymers of acrylamide and of ammonium acrylate such as PAS
5161 or BOZEPOL C from Hoechst; acrylate/octylacrylamide copolymers such
as DERMACRYL from National Starch; polyacrylamide-based polymers such as
SEPIGEL 305 from Seppic, crosslinked polymers of acrylamide and of
methacryloyloxyethyltrimethylammonium chloride, such as SALCARE SC 92 from
Allied Colloids,
magnesium aluminium silicate.
Depending on the application envisaged, the composition may furthermore
comprise a film-forming polymer. This is, in particular, the case when it
is desired to prepare a composition of the nail varnish, mascara or
eye-liner type or a haircare composition of the lacquer type. The polymers
may be dissolved or dispersed in the cosmetically acceptable medium. In
particular, the polymer may be present in the form of a solution in an
organic solvent or in the form of an aqueous dispersion of film-forming
polymer particles. The polymer may be selected from nitrocellulose,
cellulose acetobutyrate, polyvinyl butyrals, alkyd resins, polyesters,
acrylics, vinyls and/or polyurethanes. Mention may, in particular, be made
of the copolymers of (meth)acrylic acid and of at least one ester monomer
of linear, branched or cyclic (meth)acrylic acid and/or of at least one
amide monomer of linear, branched or cyclic, mono- or disubstituted
(meth)acrylic acid; (meth)acrylic acid/tert-butyl (meth)acrylate and/or
isobutyl (meth)acrylate/C.sub.1 -C.sub.4 alkyl (meth)acrylate copolymers;
(meth)acrylic acid/ethyl acrylate/methyl methacrylate terpolymers and
tetrapolymers; methyl methacrylate/butyl or ethyl acrylate/hydroxyethyl or
2-hydroxypropyl acrylate or methacrylate/(meth)acrylic acid tetrapolymers;
copolymers of acrylic acid and of C.sub.1 -C.sub.4 alkyl methacrylate;
terpolymers of vinylpyrrolidone, of acrylic acid and of C.sub.1-20 alkyl
methacrylate; amphoteric copolymers; vinyl esters of branched acids; vinyl
esters of benzoic acid; copolymers of (meth)acrylic acid and of at least
one olefinic monomer; copolymers of vinyl monoacid and/or of allylic
monoacid. Among the resins, mention may be made of resins of the
arylsulphonamide formaldehyde or arylsulphonamide epoxy type; resins of
the acrylic, styrene, styreneacrylate and vinylacrylate type.
The composition may also comprise at least one plasticizer, such as
tricresyl phosphate, benzyl benzoate, triethyl citrate, tributyl citrate,
triethyl acetyl citrate, 2-triethylhexyl acetyl citrate, camphor; glycol
ethers; castor oil oxyethylenated with 40 mol of ethylene oxide; propylene
glycol; butyl glycol; ethylene glycol monomethyl ether acetate; propylene
glycol ethers; ester ethers of propylene glycol and ethylene glycol;
esters of diacids such as diethyl, dibutyl and diisopropyl phthalates and
adipates, diethyl and dibutyl tartrates, diethyl and dibutyl succinates,
diethyl and dibutyl sebacates, diethyl, dibutyl and 2-diethylhexyl
phosphates, diethyl or dibutyl acetyl citrate; glycerol esters. The
plasticizers may generally be present in a concentration ranging from 1%
to 40% by weight relative to the total weight of the composition.
The composition according to the invention may also comprise a fatty phase,
in particular including fatty substances which are liquid at 25.degree.
C., such as oils of animal, vegetable, mineral or synthetic origin; fatty
substances which are solid at 25.degree. C., such as waxes of animal,
vegetable, mineral or synthetic origin; fatty substances in paste form;
gums; mixtures thereof.
The compositions according to the invention may thus comprise volatile
oils, which evaporate on contact with the skin but whose presence in the
cosmetic composition is useful since they make it easier to spread the
composition when it is applied to the skin. Spreading agents of this type,
referred to here as "volatile oils" are generally oils which, at
25.degree. C., have a saturated vapour pressure at least equal to 0.5
millibar (i.e. 50 Pa). Use is preferably made of oils whose flashpoint is
high enough to allow these oils to be used in formulation, and low enough
to obtain the desired evanescent effect. Oils whose flashpoint is of the
order of 40-100.degree. C. are preferably employed.
Mention may thus be made of volatile silicone oils, such as:
cyclic volatile silicones having 3 to 8, and preferably 4 to 6, silicon
atoms. Examples of these include cyclotetradimethylsiloxane,
cyclopentadimethylsiloxane or cyclohexadimethylsiloxane,
cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as
SILICONE FZ 3109 marketed by the company Union Carbide, which is a
dimethylsiloxane/methyloctylsiloxane cyclocopolymer,
linear volatile silicones having 2 to 9 silicon atoms. Examples of these
include hexamethyidisiloxane, hexylheptamethyltrisiloxane or
octylheptamethyltrisiloxane.
Mention may also be made of volatile hydrocarbon oils such as isoparaffins
and, in particular, isododecane; and fluorinated oils such as the one
marketed under the name GALDEN.RTM. (Montefluos).
Use may also be made of non-volatile oils, among which mention may be made
of:
poly(C.sub.1 -C.sub.20)alkylsiloxanes and, in particular those having
trimethylsilyl end groups, preferably those whose viscosity is less than
0.06 m.sup.2 /s, among which mention may be made of linear
polydimethylsiloxanes and alkylmethylpolysiloxanes such as
cetyidimethicone (CTFA name),
silicones modified with aliphatic and/or aromatic groups, which may or may
not contain fluorine, or with functional groups such as hydroxyl, thiol,
and/or amine groups,
phenylated silicone oils, in particular those of formula:
##STR1##
in which
R independently denotes a C.sub.1 -C.sub.30 alkyl radical, an aryl radical
or an aralkyl radical, n is an integer ranging from 0 to 100, and
m is an integer ranging from 0 to 100, with the condition that the sum of
n+m ranges from 1 to 100,
oils of animal, vegetable or mineral origin, and in particular animal or
vegetable oils formed by fatty acid esters of polyols, in particular
liquid triglycerides, for example sunflower oil, corn oil, soy bean oil,
marrow oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil, almond
oil or avocado oil; fish oils, glyceryl tricaprocaprylate, or vegetable or
animal oils of formula R.sub.1 COOR.sub.2 in which R.sub.1 represents a
higher fatty acid residue containing from 7 to 19 carbon atoms and R.sub.2
represents a branched hydrocarbon chain containing from 3 to 20 carbon
atoms, for example Purcellin oil; liquid paraffin, liquid petroleum jelly,
perhydrosqualene, wheatgerm oil, beauty-leaf oil, sesame oil, macadamia
oil, grapeseed oil, colza oil, copra oil, arachis oil, palm oil, castor
oil, jojoba oil, olive oil or cereal germ oil; fatty acid esters,
alcohols; acetylglycerides; octanoates, decanoates or ricinoleates of
alcohols or of polyalcohols; fatty acid triglycerides, glycerides;
fluorinated and perfluorinated oils.
The composition according to the invention may furthermore comprise other
fatty substances, which may be selected by the person skilled in the art
on the basis of general knowledge, so as to give the final composition the
desired properties, for example in terms of consistency and/or texture.
These additional fatty substances may be waxes, gums and/or fatty
substances in paste form of animal, vegetable, mineral or synthetic
origin, as well as mixtures thereof.
Mention may, in particular, be made of:
silicone gums,
waxes of animal, vegetable, mineral or synthetic origin, such as
microcrystalline waxes, paraffin, petrolatum, petroleum jelly, ozokerites,
montan wax; beeswax, lanolin and derivatives thereof; candellila wax,
ouricurry wax, carnauba wax, Japan wax, cocoa butter, cork fibre wax or
sugarcane wax; hydrogenated oils which are solid at 25.degree. C.,
ozokerites, fatty esters and glycerides which are solid at 25.degree. C.;
polyethylene waxes and waxes obtained by Fischer-Tropsch synthesis;
hydrogenated oils which are solid at 25.degree. C.; lanolins; fatty esters
which are solid at 25.degree. C.; silicone waxes; fluorinated waxes.
The composition according to the invention may also comprise one or more
organic solvents which are cosmetically acceptable (acceptable in terms of
tolerance, toxicology and feel). These organic solvents may represent from
0% to 98% of the total weight of the composition and may be selected from
hydrophilic organic solvents, lipophilic organic solvents, amphiphilic
solvents or mixtures thereof.
Among the hydrophilic organic solvents, mention may, for example, be made
of linear or branched lower monoalcohols having from 1 to 8 carbon atoms,
such as ethanol, propanol, butanol, isopropanol, isobutanol; polyethylene
glycols having from 6 to 80 ethylene oxides; polyols such as propylene
glycol, isoprene glycol, butylene glycol, glycerol and sorbitol; mono- or
dialkyl isosorbide in which the alkyl groups have from 1 to 5 carbon
atoms; glycol ethers such as diethylene glycol monomethyl or monoethyl
ether and propylene glycol ethers such as dipropylene glycol methyl ether.
As amphiphilic organic solvents, mention may be made of polyols such as
polypropylene glycol (PPG) derivatives such as fatty acid esters of
polypropylene glycol and fatty alcohol esters of PPG for example PPG-23
oleyl ether and PPG-36 oleate. As lipophilic organic solvents, mention
may, for example, be made of fatty esters such as diisopropyl adipates,
dioctyl adipates, alkyl benzoates, isopropyl myristate, isopropyl
palmitate, butyl stearate, hexyl laurate, isononyl isononanoate,
2-ethylhexyl palmitate, 2-hexydecyl laurate, 2-octyidecyl palmitate,
2-octyldecyl myristate, bis(2-hexylethyl) succinate, diisostearyl malate,
2-octyldodecyl lactate, glyceryl triisostearate and diglyceryl
triisostearate.
The composition may furthermore comprise a particulate phase, which may
comprise pigments and/or pearlescent agents and/or fillers customarily
used in cosmetic compositions. The term pigments should be understood to
mean white or colored, inorganic or organic particles intended to color
and/or opacify the composition. The term fillers should be understood to
mean colorless or white, inorganic or synthetic, lamellar or non-lamellar
particles intended to give the composition body or rigidity, and/or
softness, a mafte effect and uniformity when applied as make-up. The term
pearlescent agents should be understood to mean iridescent particles which
reflect light.
The pigments may be present in the composition at a level preferably
ranging from 0 to 15% by weight of the final composition, more preferably
from 8 to 10% by weight. They may be white or colored, inorganic and/or
organic, and of customary or nanometric size. Mention may be made of
titanium, zirconium or cerium dioxides, as well as zinc oxide, iron oxide
or chromium oxide, ferric blue, chromium hydrate, carbon black,
ultramarines (aluminosilicate polysulphides), manganese pyrophosphate and
certain metal powders such as those of silver or of aluminium, and carbon
black. Mention may also be made of the lakes commonly used to give a
make-up effect to the lips and the skin, these lakes being salts of
calcium, barium, aluminium or zirconium, or acidic colorants such as, for
example, haloacid, azo, and anthraquinone dyes.
The pearlescent agents may be present in the composition at a concentration
preferably ranging from 0 to 20% by weight, more preferably from 8 to 15%
by weight. Examples of the pearlescent agents which may be envisaged
include natural mother-of-pearl, mica coated with titanium oxide, with
iron oxide, with natural pigment or with bismuth oxychioride, as well as
colored titanium mica.
The fillers, which may be present at a concentration preferably ranging
from 0 to 30% by weight, more preferably 5 to 15%, in the composition, may
be inorganic or synthetic, lamellar, or non-lamellar. Mention may be made
of talc, mica, silica, kaolin, nylon powders and polyethylene powders,
Teflon, starch, boron nitride, polymer microspheres such as EXPANCEL
(Nobel Industrie), polytrap (Dow Corning) and silicone resin microbeads
(TOSPEARLS from Toshiba for example), precipitated calcium carbonate,
magnesium carbonate or hydrocarbonate, metal soaps derived from organic
carboxylic acids having from 8 to 22 carbon atoms.
Depending on the type of formulation, the pulverulent phase may represent
from 0.01 to 99% by weight of the composition.
The composition may furthermore comprise a colorant, in particular a
natural organic colorant such as cochineal carmine, and/or a synthetic
colorant such as haloacid, azo or anthraquinone dyes. Mention may also be
made of inorganic colorants such as copper sulphate.
The composition may furthermore comprise any additive customarily used in
the field of cosmetics, for example antioxidants, fragrances, essential
oils, preserving agents, lipophilic or hydrophilic cosmetic active agents,
moisturizers, vitamins, essential fatty acids, sphingolipids, self-tanning
agents such as DHA, sunscreens, anti-foaming agents, sequestering agents
and antioxidants.
Clearly, the person skilled in the art will take care to select the
optional additional compounds, and/or their amount, so that the
advantageous properties of the composition according to the invention are
not, or are not substantially, adversely affected by the addition which is
envisaged.
The cosmetic compositions may be in the form of a care and/or make-up
product for the skin, a suncare or self-tanning product, or a haircare
product. In particular, they find a particular application in the field of
lip compositions, foundations, blushers or eye-shadows, loose or compact
powders, tinted creams, eye-liners, mascaras and aqueous or solvent-based
nail varnishes.
The invention is illustrated, but in no way limited, by the following
examples.
EXAMPLE 1
The photochromic compound taken as an example was iron-doped titanium oxide
marketed by C.C.I.C. through IKEDA under the name "PHOTOGENICA 1".
Its initial characteristics were as follows:
after 30 minutes of exposure to a lamp emitting at 365 nm: .DELTA.E30=12.0
after 30 minutes of darkness: .DELTA.(.DELTA.E)=4.2
a/Heat-treatment in the Presence of LIOH
A mixture was prepared comprising iron-doped titanium oxide and 0.9% by
weight of LiOH, corresponding to 0.25% by mass of Li.sup.+. The mixture
was mechanically mixed in a mortar, then heat-treated for 4 hours in a
tube furnace at a temperature of about 800.degree. C.
The results given in the following table were obtained.
b/Heat-treatment in the Presence of Na.sub.2 O.sub.2
A mixture was prepared comprising iron-doped titanium oxide and 30% by
weight of Na.sub.2 O.sub.2, corresponding to 18% by mass of Na+. The
mixture was mechanically mixed in a mortar, then heat-treated for 4 hours
in a tube furnace at a temperature of about 800.degree. C. The results
given in the following table were obtained.
.DELTA.E30 .DELTA.(.DELTA.E)
Iron-doped titanium oxide 12.0 4.2
After treatment with LiOH 17.0 12.0
After treatment with Na.sub.2 O.sub.2 12.3 7.6
The process according to the invention therefore allows the value of
.DELTA.(.DELTA.E) to be improved while maintaining an acceptable, or even
improved, value of .DELTA.E30.
EXAMPLE 2
The following were added to pure titanium oxide of the anatase type,
dispersed in 50 ml of water:
Composition 1:--0.41% of iron in the form of FeCl.sub.3 (% calculated as
Fe.sub.2 O.sub.3 mass equivalent relative to titanium oxide), and
Composition 2:--0.41% of iron in the form of FeCl.sub.3 (% calculated as
Fe.sub.2 O.sub.3 mass equivalent relative to titanium oxide), and--0.05%
of lithium, in the form of LiOH (by mass of Li.sub.+ relative to the
titanium oxide).
The mixtures were evaporated at room temperature while being stirred, so as
to distribute the iron and lithium+iron ions uniformly, then the powder
obtained was heat-treated for 4 hours in a tube furnace at a temperature
of about 800.degree. C.
The results given in the following table were obtained.
.DELTA.E30 .DELTA.(.DELTA.E)
Composition 1: 10 5
With 0.41% of iron
Composition 2: 22.6 17.2
With 0.41% of iron +
0.05% of lithium
It is therefore seen that the treatment according to the process of the
invention makes it possible to obtain photochromic properties which are
better than those obtained according to the prior art.
EXAMPLE 3
A compact powder having the following composition is prepared:
talc 30 g
mica 20 g
BiOCl 10 g
nylon powder 16 g
zinc stearate 5 g
iron oxide 2 g
titanium oxide according to Example 1a) 10 g
fatty binder 7 g
A composition having good cosmetic properties is obtained.
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